CN108117410A - A kind of three-dimensional porous ceramics-graphene block composite material and preparation method thereof - Google Patents
A kind of three-dimensional porous ceramics-graphene block composite material and preparation method thereof Download PDFInfo
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- CN108117410A CN108117410A CN201711374220.0A CN201711374220A CN108117410A CN 108117410 A CN108117410 A CN 108117410A CN 201711374220 A CN201711374220 A CN 201711374220A CN 108117410 A CN108117410 A CN 108117410A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5001—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with carbon or carbonisable materials
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
Abstract
The invention belongs to technical field of inorganic composite material preparation, more particularly, to a kind of three-dimensional porous ceramic graphene block composite material and preparation method thereof.The preparation method includes the following steps：(1) three-dimensional porous ceramic block is immersed in the salting liquid containing the metal ion to graphene growth with catalytic action, solion is made to penetrate into the hole of the ceramic block；Surface moisture is dried after taking-up, obtains ceramic catalyst block；(2) step (1) the ceramic catalyst block is heated into reduction in a reducing atmosphere, the salt of the metal ion for containing and there is catalytic action to graphene growth is made to be reduced in the ceramic catalyst block and forms metallic particles, which is catalyst；Then vapor deposition in situ is carried out in carbonaceous gas makes graphene growth be deposited on the three-dimensional porous ceramic skeleton surface, and three-dimensional porous ceramic graphene block composite material is made.
Description
Technical field
The invention belongs to technical field of inorganic composite material preparation, more particularly, to a kind of three-dimensional porous ceramics-graphite
Alkene block composite material and preparation method thereof.
Background technology
Graphene is the two-dimensional structure that a kind of carbon atom by sp2 hydridization is formed with hexagon periodic arrangement, and thickness is only
There is 0.335nm, be the most thin but most hard material found in the world at present, while be also the basic structure of other dimension carbon materials
Unit.Geim of University of Manchester in 2004 etc. directly removes graphite crystal by using adhesive tape, successfully prepares for the first time steady
Fixed graphene allows people to have unprecedented concern to this material of graphene.Because of its unique monoatomic layer structure so that stone
Black alkene has many excellent material properties:Energy gap is 0, and light transmittance is about 97.7%, and thermal conductivity factor is up to 5300W/
(mK), electron mobility is about 2 × 105cm at room temperature2Vs, resistivity is down to 10-6Ω·cm.Graphene specific surface area
Calculated value be 2630m2/ g, intensity reach 130GPa, and Young's modulus is about 1100GPa.Its fracture strength is about 125GPa,
It is suitable with carbon nanotubes.Meanwhile unique structure makes it have room-temperature quantum Hall effect, quantum tunneling effect, bipolar electric
Field-effect and the good special natures such as electromagnetically.These excellent performances make it in the energy, microelectronics, composite material, information
And the fields such as biological medicine have great application prospect.
As what graphene was studied gos deep into, application of the graphene in ceramic base block composite material is increasingly closed
Note.Traditional ceramic matric composite uses one-dimensional carbon fiber, carbon nanotubes and ceramic whisker as enhancing phase, but these
Material disperses uneven, easily reunion in ceramic matrix；For the nano combined component of low-dimensional, graphene has more
Big advantage, such as can preferably be scattered in ceramic matrix, its excellent mechanics and physical and chemical performance, are combined in addition
In ceramic base block composite material, there are very big potentiality to improving material comprehensive performance, being hopeful to obtain has some uniquenesses
The structure-function integration block ceramic composite material of energy.For ceramics/graphene block composite material, graphene is introduced
The intensity and toughness of ceramic material can not only be enhanced in ceramic matrix, moreover it is possible to make ceramic material that there is low-density, high intensity, resist
Oxidation, it is heat-resisting wash away, the advantages that ablation resistance is excellent, moreover it is possible to assign ceramic material semiconductor, conduction, heat conduction, electrochemistry etc.
Performance can be applied in the numerous areas such as sensor, heater element, energy storage electrode.
There is ceramic powder at present and graphene is compound, the report of ceramics/graphene composite powder material, but ceramic powder
Composite graphite alkene or its preparation method are limited by there are still the poor technological deficiency of dispersion performance, agglomeration property similar to resistance to
The application of corroding electrode, calandria etc..Therefore, exploitation ceramics/graphene block composite material advantageously accounts for these and asks
Topic.For ceramics/graphene block composite material, complicated difficult due to preparing, related research is less, such composite material
The influence to material property such as preparation method, composite mode and compositely proportional does not all obtain deep system research also.
In preparation method, traditional ceramics/graphene composite material mostly using graphene oxide and ceramic powders ball milling,
Calcining, such method is difficult to control the composite quality of composite material and graphene oxide preparation has a large amount of spent acid, heavy metal ion
It generates, seriously pollutes environment, is unfavorable for technical grade production.
The content of the invention
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides a kind of three-dimensional porous ceramics-graphenes
Block composite material and preparation method thereof fully with reference to the characteristics of three-dimensional porous ceramics-graphene block composite material and needs
Ask, pointedly the preparation process of the composite material redesigned, and in preparation process key process parameter, original
Material species makes choice and optimizes, and has accordingly been prepared the three of the excellent combination properties such as a kind of good conductivity, stabilization, high intensity
Porous ceramics-graphene block composite material is tieed up, graphene and the characteristics of ceramics are combined, widened graphene and ceramics
The application prospect of composite material.
To achieve the above object, one side according to the invention provides a kind of three-dimensional porous ceramics-graphene block
The preparation method of composite material, includes the following steps：
(1) ceramics-catalyst block is prepared：
Three-dimensional porous ceramic block is handled, is made containing the metal ion to graphene growth with catalytic action
Salting liquid is penetrated into the hole of the three-dimensional porous ceramic block；Drying process after taking-up obtains ceramics-catalyst block
Body；
(2) three-dimensional porous ceramics-graphene block composite material is prepared：
Step (1) ceramics-catalyst block is heated into reduction in a reducing atmosphere, makes described contain to graphene life
The salt of the long metal ion with catalytic action reduces in the ceramics-catalyst block forms metallic particles；Then with institute
Metallic particles is stated as catalyst, carrying out being vapor-deposited in situ in carbonaceous gas, it is described three-dimensional porous to be deposited on graphene growth
Three-dimensional porous ceramics-graphene block composite material is made in ceramic skeleton surface.
Preferably, step (1) is described handles three-dimensional porous ceramic block, is specially：By three-dimensional porous ceramic block
Body is immersed in the salting liquid containing the metal ion to graphene growth with catalytic action.
Preferably, when soaking time is 2~10 small.
Preferably, step (1) it is described to graphene growth have catalytic action metal ion salting liquid be containing cobalt,
The salting liquid of iron or nickel metal ion is preferably nickel nitrate, nickel chloride, cobalt nitrate, cobalt chloride, ferric nitrate or ferric chloride solution.
Preferably, the concentration of the salting liquid is 0.1~1mol/L.
Preferably, the drying process temperature is 60~80 DEG C.
Preferably, step (2) described reducing atmosphere is hydrogen, and reduction temperature is 400~450 DEG C, the hydrogen content being passed through
For 1vol%~10vol%, the recovery time for 0.5~1 it is small when.
Preferably, step (2) described carbonaceous gas includes methane and hydrogen, further includes argon gas or nitrogen.
Preferably, the methane, hydrogen and argon gas or methane, the volume ratio of hydrogen and nitrogen are 1:2~4:30.
Preferably, the flow of the methane is 10~20SCCM.
Preferably, the temperature of step (2) described vapor deposition is 900~1050 DEG C, when sedimentation time is 2~6 small.
Other side according to the invention provides a kind of three-dimensional porous ceramics-graphene block composite material, with three
Dimension porous ceramics is skeleton, has multi-layer graphene on its ceramic skeleton surface and internal generation.
Preferably, the multi-layer graphene is 2~10 layer graphenes.
Preferably, the three-dimensional porous ceramics are the aluminium oxide with three-dimensional porous structure, zirconium oxide or cerium oxide block.
Preferably, the three-dimensional porous ceramic volumetric density is 3.81-3.93g/cm3, flexural strength 300-350MPa,
Hardness HRA is 84-92.
Preferably, the bulk density of the three-dimensional porous ceramics-graphene block composite material is 3.85-3.96g/cm3,
Flexural strength is 330-370MPa, hardness HRA：86-95.
In general, by the above technical scheme conceived by the present invention compared with prior art, it can obtain down and show
Beneficial effect：
(1) present invention proposes a kind of preparation method of three-dimensional porous ceramics-graphene block composite material, in catalyst
Catalytic action under, pass through the graphene that vapor deposition grows few layer or few layer in three-dimensional porous ceramic block surface in situ, protect
The original three-dimensional porous structure of ceramic block, while the accurate growth for controlling graphene have been held, the two is carried out to compound, maximum
The advantage using the two of limit so that the composite material being prepared shows excellent in flexural strength, hardness etc.
Performance.
(2) three-dimensional porous ceramics-graphene block composite material that the present invention is prepared by vapour deposition process in situ,
Graphene combines closely to form composite material with ceramic material surfaces, and the stability of composite material is good.
(3) three-dimensional porous ceramics-graphene block composite material provided by the invention, using porous ceramics as skeleton, graphite
Alkene growth in situ improves the electric conductivity of composite material in ceramic surface；The modification of graphene can make ceramic material have height
The advantages that intensity, anti-oxidant, resistance to erosion.
(4) preparation method of three-dimensional porous ceramics-graphene block composite material provided by the invention is simple, quick, peace
Entirely, and the material prepared need not carry out subsequent processing.Therefore the present invention provides the porous potteries with industrial applications prospect
Porcelain-graphene composite material and preparation method thereof is being catalyzed, the energy, and the application fields such as photoelectricity have bright prospects.
Description of the drawings
Fig. 1 is the preparation flow schematic diagram of three-dimensional porous ceramics/graphene composite material；
Fig. 2 is the photo figure in kind of different samples in preparation process；
Fig. 3 is the scanning electron microscope (SEM) of three-dimensional porous ceramic and three-dimensional porous ceramics/graphene composite material
Figure；
Fig. 4 is the Raman spectrogram of three-dimensional porous ceramics/graphene composite material.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Conflict is not formed each other to can be combined with each other.
The present invention provides a kind of preparation method of three-dimensional porous ceramics-graphene block composite material, including walking as follows
Suddenly：
(1) ceramics-catalyst block is prepared：
Three-dimensional porous ceramic block is handled, is made containing the metal ion to graphene growth with catalytic action
Salting liquid is penetrated into the hole of the ceramic block；Drying process after taking-up obtains ceramics-catalyst block.
Specific processing mode includes：By three-dimensional porous ceramic block be immersed in containing to graphene growth have catalysis make
In the salting liquid of metal ion or using modes such as dipping, sprayings solion is made to penetrate into the ceramic block
Hole in；Surface moisture is dried after taking-up, obtains ceramics-catalyst block；There is the gold of catalytic action to graphene growth
Belonging to the salting liquid of ion includes the salting liquid containing cobalt, iron or nickel metal ion, such as nickel nitrate, nickel chloride, cobalt nitrate, chlorination
Cobalt, ferric nitrate or ferric chloride solution, the concentration of the salting liquid is 0.1~1mol/L, and soaking time is excellent when by the way of immersion
Elect as 2~10 it is small when, drying temperature be 60~80 DEG C, dry surface moisture.
(2) three-dimensional porous ceramics-graphene block composite material is prepared：
It is first passed through inert gas and removes air, then step (1) ceramics-catalyst block is heated in a reducing atmosphere
Reduction makes the salt of the metal ion for containing and having catalytic action to graphene growth in the ceramics-catalyst block
Reduction forms metallic particles, which is catalyst；Reducing atmosphere is hydrogen, and reduction temperature is 400~450 DEG C, is passed through
Hydrogen content for 1vol%~10vol%, the recovery time for 0.5~1 it is small when.Then switch gas, be passed through carbonaceous gas,
Using the metallic particles as catalyst in carbonaceous gas, it is described three-dimensional porous that progress vapor deposition in situ is deposited on graphene growth
Ceramic skeleton surface is cooled to room temperature and three-dimensional porous ceramics-graphene block composite material is made.Carbonaceous gas includes methane
And hydrogen, argon gas or nitrogen are further included, wherein the volume ratio of the methane, hydrogen and argon gas or methane, hydrogen and nitrogen is
1:2~4:30；The flow of methane is preferably 10~20SCCM.The temperature of vapor deposition is 900~1050 DEG C, sedimentation time 2
~6 it is small when.
The present invention by first by three-dimensional porous ceramic block be immersed in containing cobalt, iron, nickel metal ion salting liquid in,
So that catalyst salt solution is penetrated into the hole of the three-dimensional porous ceramic material, then reduction makes catalysis in a reducing atmosphere
Agent salting liquid reduction generation catalyst metal particles, then heat up in the presence of containing methane, hydrogen or other gases into
Row vapor deposition in situ so that graphene growth in situ is deposited on the inner surface and the outer surface of three-dimensional porous ceramic block.
Wherein, the concentration of catalyst solution directly influences load capacity of the catalyst on three-dimensional porous ceramic skeleton surface,
Secondly the ratio of mixed gas is to influence graphene property, the factor of the number of plies in chemical gas-phase deposition system.Therefore it is final multiple
In the preparation process of condensation material, catalyst solution concentration and ratio of gas mixture are key parameters.By dense to catalyst solution
The screening of degree, load capacity is optimal to the growth result of graphene when the concentration for obtaining the salting liquid is 0.1~1mol/L.In addition
When the volume ratio of methane, hydrogen and argon gas or methane described in mixed gas, hydrogen and nitrogen is 1:2~4:30；The stream of methane
Amount preferably 10~20SCCM, obtained three-dimensional porous ceramics/graphene composite material best performance, the corresponding graphene number of plies
For few layer or few layer.
A kind of three-dimensional porous ceramics-graphene block composite material provided by the invention, is prepared according to the method described above,
It, for skeleton, has multi-layer graphene, ceramic skeleton surface refers not only to this with three-dimensional porous ceramics in its ceramic skeleton Surface Creation
The outer surface of skeleton further includes the ceramic skeleton inner surface.The three-dimensional porous ceramics that the present invention uses preferably have bulk density
For 3.81-3.93g/cm3, flexural strength 300-350MPa, hardness HRA are the ceramic skeleton of 84-92, such as with three-dimensional more
Aluminium oxide, zirconium oxide or the cerium oxide block of pore structure.The graphene is covered in ceramic skeleton surface, is to lack layer or few layer stone
Black alkene.Three-dimensional porous ceramics-graphene block composite material its bulk density being prepared by the preparation method of the present invention
Up to 3.85-3.96g/cm3, flexural strength 330-370MPa, hardness HRA are 86-95.
Chemical vapor deposition is a kind of Chemical Engineering Technology, which mainly utilizes one or more of gas containing film element
Phase compound or simple substance carry out the method that chemical reaction generates film on the surface of a substrate.And the physical function of final product can
Accurately to be controlled by the deposition process of gas phase doping.By chemical vapour deposition technique, urged using gaseous carbon source (such as methane)
Agent substrate or containing graphene is grown in catalyst substrate (such as iron, cobalt, nickel), can accurately control the growth matter of graphene
Amount, the number of plies play a crucial role the final performance for regulating and controlling composite material.Three-dimensional porous ceramics-graphite of the present invention
Alkene block composite material is kept due to growing graphene as substrate, using chemical vapour deposition technique using three-dimensional porous ceramics
Original three-dimensional porous structure, while the accurate growth for controlling graphene, the two are carried out compound, are utilized to greatest extent
The advantage of the two, therefore excellent performance is shown in flexural strength, hardness etc..
It is embodiment below：
Embodiment 1：
1) it is porous alumina ceramic block (the bulk density 3.81g/cm of 1*1*0.5cm by size3, flexural strength：
300MPa, hardness HRA：84) immerse in the nickel nitrate solution of 0.1M concentration, taken out after 2h, 60 degrees Celsius of drying evaporation superfluous waters
Point, obtain ceramics-catalyst block.
2) ceramics-catalyst bulk material is placed in tube furnace, is first passed through argon gas and removes air, be warming up to 400 again and take the photograph
1vol.% hydrogen is passed through after family name's degree, heating 0.5 makes nickel nitrate reduce to form nickel particle when small.900 degrees Celsius are warming up to again, are led to
Entering ratio is：1:2:30 methane, hydrogen, argon gas gaseous mixture, methane flow 10sccm.Grow 2 it is small when, be cooled to room temperature i.e.
It can obtain three-dimensional porous ceramics-graphene block composite material.The three-dimensional porous ceramics being prepared-graphene block composite wood
Expect its bulk density up to 3.85g/cm3, flexural strength 330MPa, hardness HRA are 86.
The present embodiment preparation flow is as shown in Figure 1, wherein three-dimensional porous ceramic, three-dimensional porous ceramics/catalyst, three-dimensional are more
Hole ceramics/graphene composite material material object optical photograph is as shown in Fig. 2, material color is deepened after compound, it was confirmed that ceramic block
Body surface face deposited grapheme material.SEM such as Fig. 3 institutes of three-dimensional porous ceramic, three-dimensional porous ceramics/graphene composite material
Show.It can be seen that, included outer surface by Fig. 3 on three-dimensional porous ceramic skeleton surface and skeletal internal pore surface grown stone
Black alkene.The Raman spectrum of three-dimensional porous ceramics/graphene composite material is as shown in figure 4, peak crystallization G peaks are significantly larger than defect peak D
Peak, it was demonstrated that its carbon crystallinity is fine, is crystalline carbon, that is, graphene.In addition, 2D peaks are stronger, pass through 2D peaks peak intensity and G peaks peak intensity
Ratio can prove that graphene is few layer or few layer (2-10 layers).
Embodiment 2：
1) by porous alumina ceramic block (the bulk density 3.93g/cm by size for 1*1*0.5cm3, anti-folding is by force
Degree：350MPa, hardness HRA：92) immerse in the nickel chloride solution of 1M concentration, impregnate 2h and take out, 80 degrees Celsius of drying evaporations are extra
Moisture obtains ceramics-catalyst block.
2) ceramics-catalyst bulk material is placed in tube furnace, is first passed through argon gas and removes air, be warming up to 450 again and take the photograph
10vol.% hydrogen is passed through after family name's degree, heating 1 makes nickel nitrate reduce to form nickel particle when small.1050 degrees Celsius are warming up to again, are led to
Entering ratio is：1:2:30 methane, hydrogen, argon gas gaseous mixture, methane flow 20sccm.Grow 6 it is small when, be cooled to room temperature i.e.
It can obtain three-dimensional porous ceramics-graphene block composite material.The three-dimensional porous ceramics being prepared-graphene block composite wood
Expect its bulk density up to 3.96g/cm3, flexural strength 370MPa, hardness HRA pass through 2D peaks peak intensity and G peaks peak intensity for 95.
Ratio can prove that graphene of the in-situ deposition on aluminium oxide ceramics skeleton is few layer or few layer (2-10 layers).
Embodiment 3：
1) by porous alumina ceramic block (the bulk density 3.86g/cm by size for 1*1*0.5cm3, anti-folding is by force
Degree：330MPa, hardness HRA：88) immerse in the cobalt chloride solution of 0.5M concentration, 2h takes out, 70 degrees Celsius of drying evaporation superfluous waters
Point, obtain ceramics-catalyst block.
2) ceramics-catalyst bulk material is placed in tube furnace, is first passed through argon gas and removes air, be warming up to 420 again and take the photograph
5vol.% hydrogen is passed through after family name's degree, heating 0.5 makes nickel nitrate reduce to form nickel particle when small.1000 degrees Celsius are warming up to again, are led to
Entering ratio is：1:2:30 methane, hydrogen, argon gas gaseous mixture, methane flow 15sccm.Grow 4 it is small when, be cooled to room temperature i.e.
It can obtain three-dimensional porous ceramics-graphene block composite material.The three-dimensional porous ceramics being prepared-graphene block composite wood
Expect its bulk density up to 3.88g/cm3, flexural strength 357MPa, hardness HRA are 88.Pass through 2D peaks peak intensity and G peaks peak intensity
Ratio can prove that graphene of the in-situ deposition on aluminium oxide ceramics skeleton is few layer or few layer (2-10 layers).
Embodiment 4：
1) by porous zirconia ceramic block (the bulk density 3.86g/cm by size for 1*1*0.5cm3, anti-folding is by force
Degree：330MPa, hardness HRA：88) immerse in the cobalt nitrate solution of 0.5M concentration, 2h takes out, 70 degrees Celsius of drying evaporation superfluous waters
Point, obtain ceramics-catalyst block.
2) ceramics-catalyst bulk material is placed in tube furnace, is first passed through argon gas and removes air, be warming up to 430 again and take the photograph
5vol.% hydrogen is passed through after family name's degree, heating 0.5 makes nickel nitrate reduce to form nickel particle when small.1000 degrees Celsius are warming up to again, are led to
Entering ratio is：1:2:30 methane, hydrogen, argon gas gaseous mixture, methane flow 12sccm.Grow 4 it is small when, be cooled to room temperature i.e.
It can obtain three-dimensional porous ceramics-graphene block composite material.The three-dimensional porous ceramics being prepared-graphene block composite wood
Expect its bulk density up to 3.91g/cm3, flexural strength 365MPa, hardness HRA are 87.Pass through 2D peaks peak intensity and G peaks peak intensity
Ratio can prove that graphene of the in-situ deposition on aluminium oxide ceramics skeleton is few layer or few layer (2-10 layers).
Embodiment 5：
1) by porous oxidation cerium ceramic block (the bulk density 3.91g/cm by size for 1*1*0.5cm3, anti-folding is by force
Degree：340MPa, hardness HRA：87) immerse in the iron nitrate solution of 0.5M concentration, 2h takes out, 70 degrees Celsius of drying evaporation superfluous waters
Point, obtain ceramics-catalyst block.
2) ceramics-catalyst bulk material is placed in tube furnace, is first passed through argon gas and removes air, be warming up to 450 again and take the photograph
5vol.% hydrogen is passed through after family name's degree, heating 0.5 makes nickel nitrate reduce to form nickel particle when small.1050 degrees Celsius are warming up to again, are led to
Entering ratio is：1:4:30 methane, hydrogen, argon gas gaseous mixture, methane flow 15sccm.Grow 4 it is small when, be cooled to room temperature i.e.
It can obtain three-dimensional porous ceramics-graphene block composite material.The three-dimensional porous ceramics being prepared-graphene block composite wood
Expect its bulk density up to 3.96g/cm3, flexural strength 350MPa, hardness HRA are 91.Pass through 2D peaks peak intensity and G peaks peak intensity
Ratio can prove that graphene of the in-situ deposition on aluminium oxide ceramics skeleton is few layer or few layer (2-10 layers).
Embodiment 6：
1) by porous alumina ceramic block (the bulk density 3.89g/cm by size for 1*1*0.5cm3, anti-folding is by force
Degree：320MPa, hardness HRA：88) immerse in the ferric chloride solution of 1M concentration, 2h takes out, 70 degrees Celsius of drying evaporation superfluous waters
Point, obtain ceramics-catalyst block.
2) ceramics-catalyst bulk material is placed in tube furnace, is first passed through argon gas and removes air, be warming up to 450 again and take the photograph
10vol.% hydrogen is passed through after family name's degree, heating 0.5 makes nickel nitrate reduce to form nickel particle when small.1000 degrees Celsius are warming up to again,
The ratio of being passed through is：1:3:30 methane, hydrogen, argon gas gaseous mixture, methane flow 20sccm.Grow 4 it is small when, be cooled to room temperature
It can obtain three-dimensional porous ceramics-graphene block composite material.Three-dimensional porous ceramics-graphene the block being prepared is compound
Its bulk density of material is up to 3.96g/cm3, flexural strength 360MPa, hardness HRA are 95.Pass through 2D peaks peak intensity and G peaks peak
Strong ratio can prove that graphene of the in-situ deposition on aluminium oxide ceramics skeleton is few layer or few layer (2-10 layers).
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of three-dimensional porous ceramics-graphene block composite material, which is characterized in that include the following steps：
(1) ceramics-catalyst block is prepared：
Three-dimensional porous ceramic block is handled, makes the salt containing the metal ion to graphene growth with catalytic action molten
Liquid is penetrated into the hole of the three-dimensional porous ceramic block；Drying process after taking-up obtains ceramics-catalyst block；
(2) three-dimensional porous ceramics-graphene block composite material is prepared：
Step (1) ceramics-catalyst block is heated into reduction in a reducing atmosphere, makes described contain to graphene growth tool
The salt for having the metal ion of catalytic action reduces in the ceramics-catalyst block forms metallic particles；Then with the gold
Metal particles are catalyst, and vapor deposition in situ is carried out in carbonaceous gas makes graphene growth be deposited on the three-dimensional porous ceramics
Three-dimensional porous ceramics-graphene block composite material is made in skeleton surface.
2. preparation method as described in claim 1, which is characterized in that step (1) is described to carry out three-dimensional porous ceramic block
Processing, specially：Three-dimensional porous ceramic block is immersed in containing the metal ion to graphene growth with catalytic action
In salting liquid.
3. preparation method as described in claim 1, which is characterized in that step (1) is described to there is catalysis to make graphene growth
The salting liquid of metal ion is the salting liquid containing cobalt, iron or nickel metal ion.
4. preparation method as described in claim 1, which is characterized in that step (2) described reducing atmosphere be hydrogen, reduction temperature
For 400~450 DEG C, the hydrogen content being passed through is 1vol%~10vol%, when the recovery time is 0.5~1 small.
5. preparation method as described in claim 1, which is characterized in that step (2) described carbonaceous gas includes methane and hydrogen,
Further include argon gas or nitrogen；Preferably, the methane, hydrogen and argon gas or methane, the volume ratio of hydrogen and nitrogen are 1:2
~4:30.
6. preparation method as described in claim 1, which is characterized in that the temperature of step (2) described vapor deposition for 900~
1050 DEG C, when sedimentation time is 2~6 small.
7. a kind of three-dimensional porous ceramics-graphene block composite material, which is characterized in that with three-dimensional porous ceramics for skeleton,
Its ceramic skeleton surface and internal generation have multi-layer graphene.
8. composite material as claimed in claim 7, which is characterized in that the multi-layer graphene is 2~10 layer graphenes.
9. composite material as claimed in claim 7, which is characterized in that the three-dimensional porous ceramics are with three-dimensional porous structure
Aluminium oxide, zirconium oxide or cerium oxide block.
10. composite material as claimed in claim 7, which is characterized in that the three-dimensional porous ceramic volumetric density is 3.81-
3.93g/cm3, flexural strength 300-350MPa, hardness HRA are 84-92.
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